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  • Cr(III)-Cr(III) interactions in two alkoxo-bridged heterometallic Zn2Cr2 complexes self-assembled from zinc oxide, Reinecke's salt, and diethanolamine.

Cr(III)-Cr(III) interactions in two alkoxo-bridged heterometallic Zn2Cr2 complexes self-assembled from zinc oxide, Reinecke's salt, and diethanolamine.

Inorganic chemistry (2010-06-15)
Valentyna V Semenaka, Oksana V Nesterova, Volodymyr N Kokozay, Viktoriya V Dyakonenko, Roman I Zubatyuk, Oleg V Shishkin, Roman Boca, Julia Jezierska, Andrew Ozarowski
RESUMEN

Two new tetranuclear complexes, [Zn(2)Cr(2)(NCS)(4)(Dea)(2)(HDea)(2)].4DMSO (1; DMSO = dimethyl sulfoxide) and [Zn(2)Cr(2)(NCS)(4)(Dea)(2)(HDea)(2)].2CH(3)CN (2), were prepared from zinc oxide, Reinecke's salt, NH(4)[Cr(NCS)(4)(NH(3))(2)].H(2)O, ammonium thiocyanate, and a nonaqueous solution of diethanolamine (H(2)Dea) in a reaction carried out under open air. Both compounds have similar centrosymmetric crystal structures based on a tetranuclear {Zn(2)Cr(2)(mu(3)-O)(2)(mu-O)(4)} core. Variable-temperature magnetic susceptibility measurements of 1 and 2 show weak antiferromagnetic coupling between chromium centers. The magnetic data and high-field, high-frequency electron paramagnetic resonance spectra were analyzed in terms of the spin Hamiltonian H = JS(1).S(2) - j(S(1).S(2) + mu(B)B{g(1)}S(1) + D(Cr){S(z1)(2) - S(1)(S(1) + 1)/3} + E(Cr)(S(x1)(2) - S(y1)(2)) + mu(B)B{g(2)}S(2) + D(Cr){S(z2)(2) - S(2)(S(2) + 1)/3} + E(Cr)(S(x2)(2) - S(y2)(2)) + D(12){S(z1)S(z2) - S(1).S(2)/3} + E(12)(S(x1)S(x2) - S(y1)S(y2)) with J = 13.7 cm(-1), j = 1.1 cm(-1), D(Cr) = 0.3864 cm(-1), E(Cr) = -0.1104 cm(-1), D(12) = -0.1873 cm(-1), and E(12) = -0.0155 cm(-1) for 1 and J = 9.4 cm(-1), j = 0.8 cm(-1), D(Cr) = 0.3564 cm(-1), E(Cr) = -0.0647 cm(-1), D(12) = -0.1850 cm(-1), and E(12) = -0.0112 cm(-1) for 2. Density functional theory (DFT) calculations were employed to calculate the zero-field splitting on Cr(3+) ions. Calculations of the exchange integrals J were attempted by using the "broken-symmetry" DFT method.

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Sigma-Aldrich
Diethanolamine, reagent grade, ≥98.0%
Sigma-Aldrich
Diethanolamine, BioUltra, ≥99.5% (GC)
Sigma-Aldrich
Diethanolamine, puriss. p.a., ACS reagent, ≥99.0% (GC)
Sigma-Aldrich
Diethanolamine, ACS reagent, ≥98.5%
Sigma-Aldrich
Diethanolamine hydrochloride, 98%
Supelco
Diethanolamine, analytical standard
Sigma-Aldrich
Diethanolamine, JIS special grade, ≥99.0%
Sigma-Aldrich
Diethanolamine, SAJ first grade, ≥98.0%